CN1125098C - Process for preparation of rubber-reinforced styrene resin - Google Patents
Process for preparation of rubber-reinforced styrene resin Download PDFInfo
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- CN1125098C CN1125098C CN98813334.2A CN98813334A CN1125098C CN 1125098 C CN1125098 C CN 1125098C CN 98813334 A CN98813334 A CN 98813334A CN 1125098 C CN1125098 C CN 1125098C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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Abstract
The present invention relates to a method for manufacturing styrene resins which are strengthened by rubber. The method comprises: polymerization equipment which is basically composed of a preliminary polymerizer, a mixing device which is connected with recycling pipe lines, a recycling reactor and a piston flow type reactor is used, raw material liquid is continuously supplied into the preliminary polymerizer for preliminary polymerization, the liquid which is obtained by the preliminary polymerization is supplied to a mixing device to mix with recycling liquid which is supplied by the flow of liquid flow which is supplied by the preliminary polymerizer to the mixing device with recycling reactor with 0.5 to 3 times (volume), rubber polymers which are contained in the obtained mixture are dispersed to granules through machine shearing force, and the obtained mixture is supplied into a plug flow reactor for polymerization. The method can constantly obtain products with high impact strength, good appearance characteristics and good coloration performance at high speed and does not change machine shearing force which influences particle diameters.
Description
Technical field
The present invention relates to a kind of method of producing rubber enhanced styrene base resin.More particularly, the present invention relates to a kind of method of producing rubber enhanced styrene base resin, this method can high-speed production have homogeneous quality, promptly has the product of excellent balance on shock strength, appearance characteristics and tinctorial property, and need not to change the mechanical shear stress that is used for control size.
Background technology
For the rubber enhanced styrene base resin of production tinctorial property, shock strength and excellent appearance, require adjusting to be scattered in the granularity and size-grade distribution and each comfortable OK range of external phase molecular weight of the rubber grain in the resin.Well-known is that the granularity of rubber grain is the essential factor of particularly important.The improvement of resin outward appearance is accompanied by reducing of rubber particle size.Yet the resin shock strength reduces with rubber particle size and reduces.It has been generally acknowledged that best rubber particle size is 0.8-3 μ m.
Usually, make the styrene solution of rubbery polymer become disperse phase and the styrene solution of polystyrene resin becomes external phase (promptly take place mutually change) and these further stand under the situation of mechanical shearing mutually in churned mechanically shearing, rubber particle size was just decided when the styrene-based monomers transformation efficiency was 5-20%.This does not change mutually and can finish immediately, but carries out on considerable time and big space.Therefore, the shearing force that reaches required rubber particle size depends on the speed of rotation of the reactor that applies shearing force, mixing tank etc. and the residence time therein.
Therefore, for by using the product of identical polymerization unit high-speed production equal in quality, need to increase the liquid storage amount that infeeds in the reactor.But in this case, the residence time in reactor shortens, and the shearing force that is stood when changing mutually simultaneously reduces, and causes granularity to increase.In order to overcome this problem, common way is to improve the agitator speed of adjusting rubber particle size with the enhancing mechanical shear stress, thereby the gained rubber particle size is adjusted to desirable value.But, should apply big shearing force in order to improve production rate greatly.Therefore need at first improve the capacity (as physical strength, moyor etc.) of equipment, because the design of equipment used, this is difficulty very.As long as guarantee physical strength to a certain degree, can increase shearing force by improving speed of rotation.But, on stagnation point, this mobile increase on sense of rotation of polymeric liquid.As a result, shearing action takes place saturated, therefore only is difficult to obtain required rubber particle size by mechanical shear stress.
In order to use the product of identical polymerization unit high-speed production equal in quality, except mechanical shear stress, also have another kind of method, it forms by the molecular weight that reduces used rubbery polymer.But the molecular weight that reduces rubbery polymer is unsatisfactory, because can make the variation such as shock strength of gained rubber enhanced styrene base resin like this.
On the other hand, the inventive method is similar to disclosed production method among the JP-A-63-113009 (term used herein " JP-A " means " unexamined Japanese Patent Application Publication ").The disclosed method of this patent application relates to by increasing the physical strength (as shock strength) that the content of styrene-based polymer in the dispersive rubber grain improves resin.Therefore, be described to wherein that to return amount of polymers in the mixing tank be per 100 weight parts infeeds polymkeric substance 12-35 weight part in the mixing tank, preferred 17-30 weight part by pre-polymerizer by recirculation reactor.In the time of in the round-robin amount of liquid drops on this scope, the rubber particle size in the product can not change and therefore can not be owing to circulation is recently boosted productivity.Therefore, the present invention is different from JP-A-63-113009 fully.
On the other hand, JP-B-59-17725 (term used herein " JP-B " means " Japanese Patent of having examined is open ") discloses a kind of production method, and this method does not relate to the used this prepolymerization step of the present invention.Use this method on the balance between shock strength, appearance characteristics and tinctorial property, not reach the object of the invention.
The purpose of this invention is to provide a kind of method of producing rubber enhanced styrene base resin, this method can high-speed production have the product of excellent balance between shock strength, appearance characteristics and tinctorial property, and does not change the mechanical shear stress that is used for control size.
Disclosure of the Invention
The inventor has carried out deep research, found that by regulate in prepolymer liquid and the circulating liquid separately polymer concentration and the ratio of mixture of these two kinds of liquid can realize above-mentioned purpose of the present invention to suitable scope.
Therefore, the invention provides a kind of method of producing rubber enhanced styrene base resin, this method comprises the following steps:
Prepolymerization contains the step of the styrene-based monomers liquid storage of 2-15wt% rubbery polymer;
With previous step rapid in prepolymerized prepolymer liquid infeed the step of recirculation reactor through mixing device;
With polymeric liquid from recirculation reactor with 0.5-3 doubly the flow of the prepolymer liquid flow rate to infeeding mixing device loop back mixing device, to mix the step of this prepolymer liquid and polymeric liquid substantially equably by this mixing device; With
In plug flow reactor, further be aggregated in the step of polymeric polymeric liquid in the recirculation reactor.
As embodiment of the present invention, can exemplify following embodiment:
The production method of the mixing tank that a kind of use comprises pre-polymerizer, connect with circulation line and the polymerization unit of recirculation reactor and plug flow reactor, this method comprises that the liquid storage that will wherein be dissolved with the 2-15wt% rubbery polymer infeeds in the pre-polymerizer continuously; Prepolymerized liquid is infeeded in the mixing tank; In this mixing tank prepolymer liquid is mixed with circulating liquid, doubly (the circular flow ratio: volume ratio) flow in the prepolymer liquid flow rate that infeeds is circulated by recirculation reactor this circulating liquid with 0.5-3; By mechanical shear stress with rubbery polymer granulation and homodisperse in blended liquid; Then polymeric liquid is infeeded in the plug flow reactor, thereby carry out polymerization;
A kind of method of producing rubber enhanced styrene base resin as mentioned above, wherein will be adjusted to 3.7A-45wt% by the polymer concentration that recirculation reactor infeeds in the circulating liquid in the mixing device, condition is that A represents the concentration (with wt% express) of rubbery polymer in liquid storage; With
A kind of method of producing rubber enhanced styrene base resin as mentioned above wherein will be adjusted to 1.2A-2.8Awt% by the polymer concentration that pre-polymerizer infeeds in the mixing device, and condition is that A represents the concentration (with wt% express) of rubbery polymer in liquid storage.
The accompanying drawing summary
Fig. 1 is the schema of equipment used among the embodiment of illustrative the inventive method.
Implement best mode of the present invention
Prepolymerization step purpose of the present invention is styrene-based monomers and rubbery polymer graft polymerization.The pre-polymerizer type is not particularly limited and can uses the pre-polymerizer that has agitating vane or have static mixer, as long as it is equipped with the mechanism that is used to eliminate reaction heat.From carrying out even grafted viewpoint at rubbery polymer, the preferred pre-polymerizer that uses with high piston flow.More particularly, preferred use is equivalent to and seldom causes back mixing and have at least 5 grades, more preferably the pre-polymerizer of at least 9 grades complete tempering tank production line model (complete mixing tank line model).
Circulation step relates to and a part is returned the step of above-mentioned mixing device from the polymeric liquid of recirculation reactor and comprise that further the polymeric liquid of the reactor of self-circulation in the future doubly returns in the mixing device to the flow of the prepolymer liquid flow rate that infeeds mixing device with 0.5-3, and equably prepolymer liquid is mixed with polymeric liquid basically by this mixing device.In addition, the mixing liquid with gained prepolymer liquid and polymeric liquid infeeds recirculation reactor and polymerization.In other words, between mixing device and recirculation reactor, form circulation line.
The circulation line that is used for the present invention comprises mixing device and recirculation reactor.The preferred cycle reactor is equipped with agitating vane.Although the device to circulating reaction liquid is not particularly limited, use pump usually.
Type to recirculation reactor there is no particular restriction, as long as it can control reaction temperature.The preferred use has the recirculation reactor of agitating vane, and can use complete hybrid reactor or plug flow reactor.Stir power and should guarantee to remove heat of polymerization and controlled temperature, and do not need to control the necessary stirring power of rubber particle size.
The structure that is used for mixing device of the present invention does not have particular restriction.Promptly can use various mixing tanks or agitator, but preferably can mix the mixing device of the dispersion of two kinds of liquid and formation rubbery polymer at short notice.Can use complete mixed type mixing tank or tower mixing tank.Also can use the mixing tank of particular type, as the HOMOMIXER (trade name) that makes by Tokushu Kakoki K.K., SMJ-30 MIXER (trade name) that makes by Sakura Seisakusho K.K. and SMJ-100 (trade name) and by the W-1 MIXER (trade name) and the U MIXER (trade name) of Satake KagakuK.K. manufacturing.Yet using the big shearing force of application is undesirable with the mixing tank or the operational condition of fracture rubber molecular chain.For example, when the tower mixing tank of clavate agitating vane was equipped with in use, preferably the average linear velocity with agitating vane was adjusted to 0.1-3.0m/sec, and the ratio of the average particle size of rubber grain and number average particle size is adjusted to was not more than 3.0.
In mixing device, rubber grain takes place to change mutually and therefore form in rubbery polymer.The capacity of used mixing tank does not have particular restriction, but is preferably the 1/5-1/20 (volume) of recirculation reactor capacity.When the mixing tank capacity is too big, mixing uniformity variation wherein.As a result, the dispersive rubber grain presents wide size-grade distribution.This is disadvantageous, because appearance characteristics and tinctorial property variation thus.On the other hand, the mixing tank capacity too hour, the residence time in mixing tank is too short.This moment two kinds of liquid can not thorough mixing and rubbery polymer can not fully distribute.This is disadvantageous, because the rubbery polymer that the problem that occurs is the finished product not to be changed pollutes, perhaps is difficult to control rubber particle size itself.As for mixer types, jitty piston flow pattern seldom is better than complete mixed type.Too many jitty may make product be polluted by the big rubber grain of dispersive, can make the appearance characteristics variation of product like this.
The plug flow reactor that is used as circulating reaction or uses in the later step of the inventive method can be the tubular reactor that the tower reactor of agitating vane is housed or built-in static mixer is housed, as long as device of energy control reaction temperature is housed for it and the flowability of polymeric liquid presents the actual piston properties of flow.In addition, can use two or more these reactors.The capacity of plug flow reactor is preferably 1-4 times of recirculation reactor, but there is no particular restriction to it.
The liquid storage that is used for the present invention is that rubbery polymer is dissolved in the solution in the styrene-based monomers.
The example of styrene-based monomers comprises vinylbenzene and α-Jia Jibenyixidanti.If need, can further contain can with the monomer of vinylbenzene or alpha-methyl styrene copolymerization, as (methyl) acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, methyl acrylate or vinyl cyanide.
The example of rubbery polymer comprises polyhutadiene, SBR, polyisoprene, paracril and natural rubber.
Containing these styrene-based monomers and rubbery polymer makes the liquid storage of main component and has following composition: 85-98wt% styrene-based monomers and 2-15wt% rubbery polymer, preferred 88-97wt% styrene-based monomers and 3-12wt% rubbery polymer, more preferably 90-97wt% styrene-based monomers and 3-10wt% rubbery polymer.If need, liquid storage can further contain polymer solvent such as ethylbenzene or toluene, and its amount is at most 15wt% based on whole liquid storage.In addition, can be to wherein adding molecular weight regulator, 10 hours half life temperatures are 70-140 ℃ initiator, as 1, two (t-butyl peroxy) hexanaphthenes, 1 of 1-, two (t-butyl peroxy)-3 of 1-, 3,5-trimethyl-cyclohexane, t-butyl-oxybenzoate, di-t-butyl peroxide, 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-and t-butyl peroxy sec.-propyl monocarbonate [PERHEXA C, PERHEXA 3M, PERBUTYL Z, PERBUTYL D, PERHEXA 25B and PERBUTYLI (trade name) are by Nippon Oils ﹠amp; Fats, Co., Ltd. makes], softening agent such as mineral oil and silicone oil, antioxidant etc.Term used herein " liquid storage " also relate to if the words of needs contain can with the styrene-based monomers copolymerization monomeric those.
When liquid storage contained polymer solvent etc., term " concentration of rubbery polymer in liquid storage " referred to the ratio of rubbery polymer and the whole solution that contains polymer solvent etc.
The term " rubber enhanced styrene base resin " that is used for production method of the present invention comprises the resin with disperse phase and external phase, wherein external phase comprises the polymkeric substance that comprises vinylbenzene, alpha-methyl styrene etc. or vinylbenzene or alpha-methyl styrene etc. and can [for example comprise (methyl) acrylate with the monomer of its copolymerization, as butyl acrylate, methyl methacrylate, butyl methacrylate, methyl acrylate etc., with vinyl cyanide] multipolymer; Disperse phase comprises the rubber grain of being made up of rubbery polymer such as polyhutadiene.
In production method of the present invention, the polymeric liquid flow that is recycled to mixing device by recirculation reactor is adjusted to 0.5-3 times of (the circular flow ratio: volume ratio) that is infeeded the prepolymer liquid flow rate in this mixing tank by pre-polymerizer, preferred 0.7-2.7 times, more preferably 0.8-2.5 doubly.When this ratio was lower than 0.5, circulating liquid only contained a small amount of fully grafting and is used as the rubbery polymer of tensio-active agent.Rubbery polymer is dispersed in unsatisfactorily in the mixing tank and therefore and can not forms complete particle as a result, causes production rate to reduce.In this case, size-grade distribution becomes extremely wide and therefore makes the appearance characteristics variation.In addition, reduce unfriendly, cause tinctorial property poor in rubber grain grafting amount at the interface.On the other hand, when aforementioned proportion surpassed 3, residence time shortening and polymer concentration in mixing tank were too high.This makes the undercompounding of prepolymer liquid and circulating liquid, is difficult to the granularity control of rubbery polymer within the required range.Production rate reduces as a result.In addition, metamorphosis and tinctorial property variation take place in the polymer moieties ground that mixes in the rubber grain.
In production method of the present invention, preferably the concentration (Awt%) that is adjusted to respect to rubbery polymer in the liquid storage of the polymer concentration in the circulating liquid that will be infeeded by recirculation reactor is 3.7A-45wt%, more preferably 4.0A-42wt%, further preferred 4.2A-40wt%.When polymer concentration was lower than 3.7A, this mixing device is dispersion rubber shaped polymer and therefore can not form complete particle fully.Therefore, in this case, for rubber particle size control within the required range, production rate can reduce.In addition, size-grade distribution can broaden, and this is disadvantageous from appearance characteristics and tinctorial property.On the other hand, when polymer concentration surpassed 45wt%, the viscosity differences between prepolymer liquid and the circulating liquid was excessive.As a result prepolymer liquid can not with the circulating liquid thorough mixing and therefore the granularity of rubbery polymer be difficult to control within the required range.Therefore, production rate can reduce.In addition, metamorphosis takes place in the polymer moieties ground that mixes in the rubber grain, and this is disadvantageous from tinctorial property.
In pre-polymerizer, preferably carry out prepolymerization and be 1.2A-2.8Awt% with respect to the concentration (Awt%) of rubbery polymer in the liquid storage so that infeed polymer concentration in the prepolymer liquid in the mixing device, more preferably 1.2A-2.6Awt%, more preferably 1.2A-2.4Awt%.When polymer concentration was lower than 1.2A, polymkeric substance was only a small amount of with the rubbery polymer grafting and so be difficult to obtain small grain size.Production rate reduces as a result.This also is disadvantageous in view of the balance between physical strength, appearance characteristics and the tinctorial property.On the other hand, when polymer concentration surpasses 2.8A, be difficult in mixing device inner control granularity and therefore reduce production rate.In addition, size-grade distribution broadens, and this is disadvantageous from appearance characteristics.
" polymer concentration " of the term of Shi Yonging in pre-polymerizer, recirculation reactor or plug flow reactor refers to by the styrene base resin that forms with the rubbery polymer polymerization and the weight ratio of each solution in the present invention.That is to say that its is represented by the dry polymeric that also dry sedimentary thus polymkeric substance in a large amount of methyl alcohol adding polymeric liquids is obtained and the ratio (wt%) of each polymeric liquid.
In accordance with the present production process, prepolymer liquid that can be by will infeeding mixing device by pre-polymerizer be adjusted in from the throughput ratio of the circulating liquid of recirculation reactor (circular flow than) as in the determined scope of essential feature of the present invention and high-speed production has the product of required rubber particle size and well balanced shock strength, appearance characteristics and tinctorial property.
In production method of the present invention, the polymeric liquid polymer concentration in plug flow reactor exit that preferably will be after being used for recirculation reactor is controlled to be 75wt% at least.When this polymer concentration was lower than 75wt%, the load that is applied on the recovery system became big, is difficult to the crosslinking degree of control rubber grain in addition.Will be from plug flow reactor effusive polymeric liquid imports in the recovery system, in this system unreacted monomer, polymer solvent etc. be removed and remaining polymkeric substance by granulation.
In rubber enhanced styrene base resin of the present invention, can in liquid storage, add additive, perhaps add in polymerization procedure, recycling step or the granulation step.The example of additive comprises those that are usually used in styrene base resin, and oxidation inhibitor for example is as the IRGANOX 1076 (trade name) that Ciba-Geigy AG makes, softening agent such as mineral oil, releasing agent such as stearic acid and Zinic stearas, tinting material, oxidation inhibitor, fire retardant etc.In addition, pellet can be mixed in forcing machine with these additives.
In each reactor, can be by the amount of suitable controlled temperature, initiator or other additives, when making styrene base resin common carry out, telomerized polymer concentration.Temperature is 90-120 ℃ in pre-polymerizer, is 90-140 ℃ in recirculation reactor, is 110-170 ℃ in plug flow reactor.Embodiment
The present invention illustrates in greater detail with reference to following examples.The measuring method of physicals etc. is as follows.(a) polymer concentration
With the accurate weighing of 5g polymeric liquid and to wherein adding about 20cc methyl alcohol.In vacuum drier in heating under 200 ℃ and the 10mmHg after 20 minutes, the resistates and calculate solid content (wt%) of accurately weighing.(b) rubber particle size (RPS)
Use Coulter counter as described below (Coulter Corporation manufacturing) to measure:
Machine body: II type Multisizer
Measuring unit: IIE type Multisizer
Equal 50% mean radius of electrolytes determined body that use is made up of dimethyl formamide and ammonium thiocyanate.(above-mentioned II type and IIE type be corresponding 2 types and 2E type respectively.) (c) izod intensity
Pressing ASTM D6381 measures.(d) appearance characteristics
At the die temperature compacted under dumb bell sample of 220 ℃ mold temperatures and 60 ℃, press JISZ8741 and estimate position apart from cast gate 5cm place.(e) tinctorial property
True quantitative orchil is added in the pellet.Under 200-220 ℃ by the single screw extrusion machine extrusioning mixture after, use injection moulding machine at 60 ℃ die temperature and 180-220 ℃ mold temperature compacted under sheet material (9mm * 5mm * 2mm).This sheet material of visual inspection compares color depth then, thereby estimates tinctorial property.
Equipment used herein is as follows.
Fig. 1 is the schema of equipment used among illustrative the inventive method embodiment.
The liquid storage that will prepare in container for storing liquid (1) is infeeded in the pre-polymerizer (3) by liquid storage charging pump (2).Diameter) and the plug flow reactor of 10 grades of excellent type agitating vanes is housed pre-polymerizer (3) is 1 liter and the L/D value (L: length, D: that is 10 for capacity.To introduce in the mixing tank (5) from the prepolymer liquid of pre-polymerizer (3).This mixing tank (5) is that 0.5 liter and L/D value are 10 and the plug flow reactor of 5 grades of bar-shaped agitating vanes is housed for capacity.To introduce in the recirculation reactor (7) through circulation line (4) from the polymeric liquid of this mixing tank.This recirculation reactor (7) is that 6 liters and L/D value are 10 and the plug flow reactor of 30 grades of bar-shaped agitating vanes is housed for capacity.
By recycle pump (6) polymeric liquid of a part from recirculation reactor (7) is recycled in the mixing tank (5) through circulation line (4).On the other hand, remaining polymeric liquid is introduced in reactor (8) and the reactor (9) successively.Reactor (8) has identical structure and capacity with (9) with recirculation reactor (7).Pre-polymerizer, mixing tank and reactor (7), (8) and (9) are equipped with external jacket separately, can be by the steam controlled temperature by this chuck.
The polymeric liquid of autoreactor (9) is introduced in the exhaust twin screw extruder (10) in the future, removes polymer solvent, unreacted monomer etc. therein.The rubber enhanced styrene base resin granulation that to discharge by twin screw extruder.Under situation shown in Figure 1, claim 1 described " circulation line " is made up of mixing tank (5) and recirculation reactor (7), and claim 1 described " plug flow reactor " is made up of reactor (8) and (9).Embodiment 1-4
In each composition shown in the table 1, add organo-peroxide 1, two (t-butyl peroxy) hexanaphthene (the PERHEXA C (trade name) of 1-, by Nippon Oils and Fats Co., Ltd makes) so that its concentration is 150ppm, prepare liquid storage thus in container for storing liquid (1).Then this liquid storage is infeeded in the pre-polymerizer.As rubbery polymer, and the use polyhutadiene (DIENE 55 (trade name), the viscosity of 5wt% styrene solution is 1650mPa s (165cps), by Asahi ChemicalIndustry Co., Ltd. makes).Use the alpha-methyl styrene dimer as molecular weight regulator.Temperature in the mixing tank is transferred to about 80 ℃.On the other hand, the temperature in control pre-polymerizer, recirculation reactor and plug flow reactor (8) and (9) is so that streamwise has the thermograde shown in the table 1.The polymer concentration in end reaction device exit is adjusted to about 80wt%.The speed of rotation of agitator in pre-polymerizer (3), mixing tank (5), recirculation reactor (7) and plug flow reactor (8) and (9) is set at is constant at 50rpm respectively, 200rpm, 50rpm, 20rpm and 5rpm.The feeding rate of control liquid storage is so that the rubber particle size of product is 1.8 μ m.The production rate of equal in quality product relatively is provided under these conditions.Table 2 shows the physicals and the production rate of the rubber enhanced styrene base resin that so obtains.Embodiment 5-9
Repeat the program of embodiment 3 under the same conditions, different is changes condition shown in polymer concentration in the recirculation reactor and the use table 1 to obtain like products.The table 2 that the results are shown in about physicals and production rate.Embodiment 10-12
Repeat the program of embodiment 3 under the same conditions, different is changes condition shown in polymer concentration in the pre-polymerizer and the use table 1 to obtain like products.About the result of physicals and production rate illustrates table 2.Comparative Examples 1-3
Repeat the program of embodiment 3 under the same conditions, different is to change condition shown in recycle ratio and the use table 1.The table 2 that the results are shown in about physicals and production rate.
In Comparative Examples 1, use the feeding rate identical with embodiment 3.Yet the gained rubber particle size surpasses target size (1.8 μ m) and therefore can not obtain the product identical with embodiment 3.
In Comparative Examples 2, reduce feeding rate to obtain target rubber particle size (1.8 μ m).Feeding rate becomes 2.6 liters/hour as a result, and embodiment 3 is 5.4 liters/hour.The production rate (3.9kg/ hour) that is reached among production rate among this embodiment (1.8kg/ hour) and the embodiment 3 is compared extremely low.The appearance characteristics of products obtained therefrom and tinctorial property are also poor.
In Comparative Examples 3, compare with embodiment 3 (5.4 liters/hour), feeding rate is reduced to 2.0 liters/hour.Therefore yet rubber particle size can not be reduced to target size (1.8 μ m) and can not obtain the product identical with embodiment 3.Comparative Examples 4
Repeat down the program of embodiment 3 under the same conditions, different is not use pre-polymerizer, but directly infeed liquid storage in the mixing tank and use table 1 shown in condition.The table 2 that the results are shown in about physicals and production rate.Compare with the product of embodiment 3, the physicals of the product that so obtains, especially izod intensity is poor.Comparative Examples 5
Repeat the program of embodiment 3 under the same conditions, different is not use mixing tank, but make prepolymer liquid with flow from the circulating liquid of recirculation reactor by circulation line and use table 1 shown in condition.The table 2 that the results are shown in about physicals and production rate.Can not obtain the having targeted particle size product of (1.8 μ m).
Table 1
| Feeding rate (L/hr) | Liquid storage is formed | The pre-polymerizer temperature (℃) | The circulating reaction actuator temperature (℃) | The plug flow reactor temperature (℃) | ||||
| Vinylbenzene (wt.%) | Rubbery polymer (wt.%) | Ethylbenzene (wt.%) | M.W. conditioning agent (ppm) | |||||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 | 3.8 4.3 5.4 4.0 | 85.0 86.0 88.0 86.0 | 6.0 6.0 6.0 6.0 | 9.0 8.0 6.0 8.0 | 700 500 100 600 | 100-110 105-115 110-120 100-110 | 110-120 115-125 125-135 115-125 | 125-155 130-160 140-170 125-155 |
| Embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 | 2.8 3.3 5.0 3.3 2.7 | 84.0 85.0 88.0 85.0 84.0 | 6.0 6.0 6.0 6.0 6.0 | 10.0 9.0 6.0 9.0 10.0 | 1000 800 100 800 1100 | 95-105 100-110 110-120 100-110 95-105 | 100-110 105-115 130-140 115-125 115-125 | 120-150 125-155 135-165 120-150 115-145 |
| Embodiment 10 embodiment 11 embodiment 12 | 4.6 4.2 2.8 | 88.0 86.0 84.0 | 6.0 6.0 6.0 | 6.0 8.0 10.0 | 300 500 1000 | 105-115 110-120 115-125 | 125-135 115-125 115-125 | 140-170 130-160 130-160 |
| Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 | 5.4 2.6 2.0 | 88.0 83.0 81.0 | 6.0 6.0 6.0 | 6.0 11.0 13.0 | 100 1100 2000 | 110-120 95-105 90-100 | 125-135 105-115 100-110 | 140-170 115-145 110-140 |
| Comparative Examples 4 Comparative Examples 5 | 3.1 2.0 | 84.0 81.0 | 6.0 6.0 | 10.0 13.0 | 900 2000 | - 90-100 | 115-125 100-110 | 120-150 110-140 |
Table 2
| Feeding rate (L/hr) | Circular flow is than (volume) | Polymer concentration (wt.%) from the circulating liquid of recirculation reactor | Polymer concentration (wt.%) from the liquid of pre-polymerizer | Particulate size (μ m) from pre-polymerizer | Izod impact strength (kg-cm/cm) | Outward appearance (Z) | Painted (naked eyes) | The granularity of product (μ m) | 1.8 the production rate (kg/hr) of μ m product | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 | 3.8 4.3 5.4 4.0 | 0.5 0.7 1.5 2.7 | 30.0 30.0 30.0 30.0 | 12.0 12.0 12.0 12.0 | 1.9 2.0 1.9 1.9 | 9.8 9.8 10.0 10.1 | 61 62 64 61 | ● ● ● ● | 1.8 1.8 1.8 1.8 | 2.7 3.1 3.9 2.9 |
| Embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 | 2.8 3.3 5.0 3.3 2.7 | 1.5 1.5 1.5 1.5 1.5 | 21.0 23.0 35.0 42.0 47.0 | 12.0 12.0 12.0 12.0 12.0 | 2.2 2.0 1.9 2.0 2.0 | 9.5 9.7 10.0 10.1 9.6 | 59 61 63 61 59 | ◎ ● ● ● ◎ | 1.8 1.8 1.8 1.8 1.8 | 2.0 2.4 3.6 2.4 2.0 |
| Embodiment 10 embodiment 11 embodiment 12 | 4.6 4.2 2.8 | 1.5 1.5 1.5 | 30.0 30.0 30.0 | 7.5 15.0 18.0 | 2.0 1.9 1.9 | 9.7 9.8 9.6 | 62 62 58 | ● ● ◎ | 1.8 1.8 1.8 | 3.3 3.0 2.0 |
| Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 | 5.4 2.6 2.0 | 0.3 0.3 4.2 | 30.0 30.0 30.0 | 12.0 12.0 12.0 | 2.7 2.2 2.6 | 9.3 9.4 9.2 | 44 54 46 | × × × | 2.6 1.8 2.5 | - 1.8 - |
| Comparative Examples 4 Comparative Examples 5 | 3.1 2.0 | 1.5 1.5 | 30.0 30.0 | - 12.0 | 1.9 2.4 | 8.0 9.0 | 55 49 | × × | 1.8 2.3 | 2.2 - |
Painted: ●: excellence, ◎: good, *: poor
Industrial applicability:
In production method of the present invention, the mixing ratio of the polymer concentration in the polymer concentration in the prepolymer liquid, the circulation liquid and these two kinds of liquid is adjusted in the suitable scope separately, and applies uniform mechanical shear stress by mixing arrangement. Therefore, can produce the product that between impact strength, holding property of outward appearance and tinctorial property, has excellent balance. In addition, even the product of these functional balances also can high-speed production under constant mechanical shear stress. Conventional art inaccessiable these advantages by control so that the rubber-like polymer in the prepolymer liquid connects suitably that skill, prepolymer liquid and the ratio of viscosities of circulation liquid are beneficial to mix in OK range and reach by using its rubber particle that connects skill capacity rubber-like polymer that the flow-rate ratio of prepolymer liquid and circulation liquid is adjusted in the OK range. In order to improve speed of production, common way is to improve mechanical shear stress. On the contrary, according to the inventive method, even be issued to high production speed at constant mechanical shear stress. Therefore, can use the blender of size reduction in the present invention, thereby bring large economic advantages.
Claims (7)
1. method of producing rubber enhanced styrene base resin may further comprise the steps:
Prepolymerization contains the step of the styrene-based monomers liquid storage of 2-15wt% rubbery polymer;
Prepolymerized prepolymer liquid in the step is in the above infeeded the step of recirculation reactor through mixing device;
Doubly polymeric liquid is circulated back to the mixing device step with uniform mixing prepolymer liquid and polymeric liquid from recirculation reactor with 0.5-3 to the flow of the prepolymer liquid flow rate that infeeds mixing device; With
Will be in recirculation reactor polymeric polymeric liquid further step of polymerization in plug flow reactor.
2. according to the method for the production rubber enhanced styrene base resin of claim 1, this method uses the recirculation reactor that comprises pre-polymerizer, mixing device, link to each other with this mixing device through circulation line and the polymerization unit of plug flow reactor to carry out.
3. according to the method for the production rubber enhanced styrene base resin of claim 1 or 2, wherein by mechanical shear stress with rubbery polymer granulation and dispersion contained in the mixing liquid in the mixing device.
4. according to the method for the production rubber enhanced styrene base resin of claim 1 or 2, wherein prepolymerization step carries out in the plug flow polymerization reactor.
5. according to the method for the production rubber enhanced styrene base resin of claim 1 or 2, wherein recirculation reactor is a plug flow reactor.
6. according to the method for the production rubber enhanced styrene base resin of claim 1 or 2, wherein will be adjusted to 3.7A-45wt% by the polymer concentration that recirculation reactor infeeds in the circulating liquid in the mixing device, condition is the concentration (representing with wt%) that A represents rubbery polymer in the liquid storage.
7. according to the method for the production rubber enhanced styrene base resin of claim 1 or 2, wherein will be adjusted to 1.2A-2.8Awt% by the polymer concentration that pre-polymerizer infeeds in the mixing device, condition is the concentration (representing with wt%) that A represents rubbery polymer in the liquid storage.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1998/002489 WO1999062976A1 (en) | 1998-06-04 | 1998-06-04 | Process for the preparation of rubber-reinforced styrene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1307604A CN1307604A (en) | 2001-08-08 |
| CN1125098C true CN1125098C (en) | 2003-10-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98813334.2A Expired - Fee Related CN1125098C (en) | 1998-06-04 | 1998-06-04 | Process for preparation of rubber-reinforced styrene resin |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6399711B1 (en) |
| JP (1) | JP3207207B2 (en) |
| CN (1) | CN1125098C (en) |
| HK (1) | HK1038760A1 (en) |
| WO (1) | WO1999062976A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1314260B1 (en) * | 1999-12-03 | 2002-12-06 | Enichem Spa | PROCEDURE FOR THE PRODUCTION OF VINYLAROMATIC POLYMERS EVENTUALLY CONTAINING AN ETHYLENICALLY UNSATURATED NITRILE. |
| US6569941B2 (en) * | 2001-03-30 | 2003-05-27 | Fina Technology, Inc. | Process for manufacturing impact resistant monovinylaromatic polymers |
| US20110054123A1 (en) * | 2009-08-26 | 2011-03-03 | Fina Technology, Inc. | High Impact Polymers and Methods of Making and Using Same |
| CA3128681A1 (en) * | 2020-08-21 | 2022-02-21 | Building Materials Investment Corporation | Roofing materials with improved low temperature sealant performance and methods of making thereof |
| CN114870750B (en) * | 2022-06-10 | 2023-09-15 | 大连理工大学 | HIPS resin production process system containing internal circulation device and high-performance HIPS resin preparation method |
| CN114870781B (en) * | 2022-06-10 | 2023-06-30 | 大连理工大学 | ABS resin production process system containing internal circulation device and preparation method thereof |
| CN116333224B (en) * | 2023-01-04 | 2024-01-23 | 常州瑞华化工工程技术股份有限公司 | Preparation method of high-impact-strength polystyrene and high-impact-strength polystyrene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63113009A (en) * | 1986-10-31 | 1988-05-18 | Nippon Steel Chem Co Ltd | Production of rubber modified styrenic resin |
| JPS63118315A (en) * | 1986-11-07 | 1988-05-23 | Nippon Steel Chem Co Ltd | Production of impact-resistant styrene resin |
| JPH0714989B2 (en) * | 1989-03-10 | 1995-02-22 | 新日鐵化学株式会社 | Method for producing rubber-modified styrenic resin |
| JPH06192346A (en) * | 1992-12-25 | 1994-07-12 | Nippon Steel Chem Co Ltd | Production of abs resin |
-
1998
- 1998-06-04 CN CN98813334.2A patent/CN1125098C/en not_active Expired - Fee Related
- 1998-06-04 US US09/555,628 patent/US6399711B1/en not_active Expired - Fee Related
- 1998-06-04 JP JP56025999A patent/JP3207207B2/en not_active Expired - Lifetime
- 1998-06-04 WO PCT/JP1998/002489 patent/WO1999062976A1/en active Application Filing
-
2001
- 2001-12-27 HK HK00109102A patent/HK1038760A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1307604A (en) | 2001-08-08 |
| JP3207207B2 (en) | 2001-09-10 |
| WO1999062976A1 (en) | 1999-12-09 |
| HK1038760A1 (en) | 2002-03-28 |
| US6399711B1 (en) | 2002-06-04 |
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